Consecutive D-Band Center Regulation of Yolk-Shell Co₈FeS₈-Fe_xC_y for Enhanced Water Oxidation and Microwave Absorption

Abstract

Electronic modulation for balancing oxygen intermediates bending energy over oxygen evolution catalytic active sites is one of the most critical factors but still remains challenging. In this case, yolk-shell Co₈FeS₈-Fe_xC_y was constructed by fast Joule-heating process with dual-ligand PBA as precursor. With the help of Spherical aberration corrected STEM, synchrotron-radiation photoelectron spectroscopy as well as DFT calculations, the consecutive manipulation of d-band center for the designed series of Co₈FeS₈-based samples by introducing the Fe_xC_y with varying element ratios was disclosed. The findings confirm that electron modulation of Co₈FeS₈-Fe_xC_y can upshift the d-band center toward Fermi level to optimize antibonding-orbital occupancy of the metal-O bond, thereby prominently minimizing Gibbs free energy for intermediates in the rate-determining step. Encouragingly, the optimal Co₈FeS₈-Fe₇C₃ delivers a significant overpotential (η₁₀) decrease by 118 mV compared with Co₈FeS₈-C, ultrasmall Tafel slope of 33.4 mV dec⁻¹, along with excellent catalytic durability. Furthermore, it also shows enhanced electromagnetic wave dissipation ability with the minimum reflection loss of −50.72 at 2.03 mm and effective absorption bandwidth of 7.87 GHz at 1.7 mm. This work uncovered the intrinsic regulation mechanism of microcomponent design and opens up a promising prospect for exploring advanced multifunctional materials.

Keywords

d-band center / electronic modulation / microwave absorption / OER / yolk-shell structure

References

[1] R. R. Zhang, L. Pan, B. B. Guo, Z. F. Huang, Z. Chen, L. Wang, X. Zhang, Z. Guo, W. Xu, K. P. Loh, J. J. Zou, J. Am. Chem. Soc. 2023, 145, 2271.

[2] M. Cui, C. Yang, B. Li, Q. Dong, M. Wu, S. Hwang, H. Xie, X. Wang, G. Wang, L. Hu, Adv. Energy Mater. 2020, 11, 2002887.

[3] F. N. I. Sari, Y. C. Lai, Y. J. Huang, X. Y. Wei, H. Pourzolfaghar, Y. H. Chang, M. Ghufron, Y. Y. Li, Y. H. Su, O. Clemens, J. M. Ting, Adv. Funct. Mater. 2024, 34, 2310181.

[4] T. X. Nguyen, Y.-H. Su, C. C. Lin, J.-M. Ting, Adv. Funct. Mater. 2021, 31, 2106229.

[5] Y. N. Guo, J. W. Yi, J. Henzie, J. H. Kim, Z. L. Wang, B. Jiang, Y. S. Bando, Y. Sugahara, J. Tang, Y. Yamauchi, Adv. Mater. 2019, 31, 1807134.

[6] S. Li, B. Chen, Y. Wang, M. Y. Ye, P. A. Aken, C. Cheng, A. Thomas, Nat. Mater. 2021, 20, 1240.

[7] M. Hou, L. Zheng, D. Zhao, X. Tan, W. Feng, J. Fu, T. Wei, M. Cao, J. Zhang, C. Chen, Nat. Commun. 2024, 15, 1342.

[8] S. Deng, Y. Zhong, Y. Zeng, Y. Wang, X. Wang, X. Lu, X. Xia, J. Tu, Adv. Sci. 2018, 5, 1700772.

[9] Y. Yang, H. Yao, Z. Yu, S. M. Islam, H. He, M. Yuan, Y. Yue, K. Xu, W. Hao, G. Sun, H. Li, S. Ma, P. Zapol, M. G. Kanatzidis, J. Am. Chem. Soc. 2019, 141, 10417.

[10] N. Yao, G. Wang, H. Jia, J. Yin, H. Cong, S. Chen, W. Luo, Angew. Chem. Int. Ed. 2022, 61, e202117178.

[11] B. Wang, Y. Hu, B. Yu, X. Zhang, D. Yang, Y. Chen, J. Power Sources 2019, 433, 126688.

[12] B. Wang, Y. Chen, G. Liu, D. Liu, Y. Liu, C. Ge, L. Wang, Z. Wang, R. Wu, L. Wang, Appl. Catal. B Environ. 2024, 341, 123294.

[13] Z. Wang, Z. Lin, J. Deng, S. Shen, F. Meng, J. Zhang, Q. Zhang, W. Zhong, L. Gu, Adv. Energy Mater. 2020, 11, 2003023.

[14] C. Hao, Y. Wu, X. Zheng, Y. Du, Y. Fan, W. Pang, A. Tadich, S. Zhang, T. Frauenheim, T. Ma, X. Li, Z. Cheng, Adv. Sci. 2024, 12, 2409842.

[15] J. Xu, X. Zhang, X. Wang, J. Zhang, J. Yu, H. Yu, ACS Catal. 2024, 14, 15444.

[16] K. Chang, D. T. Tran, J. Q. Wang, K. X. Dong, S. Prabhakaran, D. Kim, N. H. Kim, J. H. Lee, Appl. Catal. B Environ. 2023, 338, 123016.

[17] J. Diao, Y. Qiu, S. Liu, W. Wang, K. Chen, H. Li, W. Yuan, Y. Qu, X. Guo, Adv. Mater. 2019, 32, 1905679.

[18] Q. Zhou, C. Xu, J. Hou, W. Ma, T. Jian, S. Yan, H. Liu, Nano-Micro Lett. 2023, 15, 95.

[19] L. Chai, Z. Hu, X. Wang, L. Zhang, T.-T. Li, Y. Hu, J. Pan, J. Qian, S. Huang, Carbon 2021, 174, 531.

[20] G. L. Wen, H. J. Niu, A. J. Wang, Z. Z. Yin, Q. L. Zhang, J. J. Feng, J. Colloid Interface Sci. 2019, 556, 352.

[21] Q. Chang, C. Zhang, C. Liu, Y. Wei, A. V. Cheruvathur, A. I. Dugulan, J. W. Niemantsverdriet, X. Liu, Y. He, M. Qing, L. Zheng, Y. Yun, Y. Yang, Y. Li, ACS Catal. 2018, 8, 3304.

[22] Z. Gao, C. Chen, J. Chang, L. Chen, P. Wang, D. Wu, F. Xu, K. Jiang, Chem. Eng. J. 2018, 343, 572.

[23] Y. Li, W. Gao, M. Peng, J. Zhang, J. Sun, Y. Xu, S. Hong, X. Liu, X. Liu, M. Wei, B. Zhang, D. Ma, Nat. Commun. 2020, 11, 61.

[24] E. T. C. Vogt, D. Fu, B. M. Weckhuysen, Angew. Chem. Int. Ed. 2023, 62, e202300319.

[25] D. W. Kim, J. Kim, J. H. Choi, D. H. Jung, J. K. Kang, Adv. Sci. 2024, 11, 2408869.

[26] T. Wu, S. Sun, J. Song, S. Xi, Y. Du, B. Chen, W. A. Sasangka, H. Liao, C. L. Gan, G. G. Scherer, L. Zeng, H. Wang, H. Li, A. Grimaud, Z. J. Xu, Nat. Catal. 2019, 2, 763.

[27] Z. W. Chen, J. Li, P. Ou, J. E. Huang, Z. Wen, L. Chen, X. Yao, G. Cai, C. C. Yang, C. V. Singh, Q. Jiang, Nat. Commun. 2024, 15, 359.

[28] K. Zhang, Y. Liu, Y. Liu, Y. Yan, G. Ma, B. Zhong, R. Che, X. Huang, Nano-Micro Lett. 2024, 16, 66.

[29] J. Quílez-Bermejo, A. Daouli, S. G. Dalí, Y. Cui, A. Zitolo, J. Castro-Gutiérrez, M. Emo, M. T. Izquierdo, W. Mustain, M. Badawi, A. Celzard, V. Fierro, Adv. Funct. Mater. 2024, 34, 2403810.

[30] Y. Xue, B. Huang, Y. Yi, Y. Guo, Z. Zuo, Y. Li, Z. Jia, H. Liu, Y. Li, Nat. Commun. 2018, 9, 1460.

[31] Y. Li, Y. Xu, S. Chen, X. Shi, Q. Gu, L. Wang, M. Gu, B. Teng, B. Yang, J. Lu, Angew. Chem. Int. Ed. 2024, 63, e202413043.

[32] L. Wang, X. Yu, X. Li, J. Zhang, M. Wang, R. Che, Chem. Eng. J. 2020, 383, 123099.

[33] H. Liu, J. Cheng, W. He, Y. Li, J. Mao, X. Zheng, C. Chen, C. Chen, C. Cui, Q. Hao, Appl. Catal. B Environ. 2022, 304, 120935.

[34] W. Yao, W. Zheng, J. Xu, C. Tian, K. Han, W. Sun, S. Xiao, ACS Nano 2021, 15, 7114.

[35] J. Zhou, P. Li, X. Xia, Y. Zhao, Z. Hu, Y. Xie, L. Yang, Y. Liu, Y. Du, Q. Zhou, L. Yu, Y. Yu, Appl. Catal. B Environ. Energy 2024, 359, 124461.

[36] R. Wang, J. Liu, J. Xie, Z. Cai, Y. Yu, Z. Zhang, X. Meng, C. Wang, X. Xu, J. Zou, Appl. Catal. B Environ. 2022, 324, 122230.

[37] L. Yan, B. Xie, C. Yang, Y. Wang, J. Ning, Y. Zhong, Y. Hu, Adv. Energy Mater. 2023, 13, 2204245.

[38] Y. Xing, S. Liu, Y. Liu, X. Xiao, Y. Li, Z. Wang, Y. Hu, B. Xin, H. Wang, C. Wang, Nano Energy 2024, 123, 109402.

[39] Y. Liu, Y. Chen, Y. Tian, T. Sakthivel, H. Liu, S. Guo, H. Zeng, Z. Dai, Adv. Mater. 2022, 34, 2203615.

[40] Q. Wang, X. Huang, Z. L. Zhao, M. Wang, B. Xiang, J. Li, Z. Feng, H. Xu, M. Gu, J. Am. Chem. Soc. 2020, 142, 7425.

[41] J. Cao, D. Zhang, B. Ren, P. Song, W. Xu, Energy Environ. Sci. 2024, 17, 5911.

[42] H. Wua, Z. Li, Z. Wang, Y. Ma, S. Huang, F. Ding, F. Li, Q. Zhai, Y. Ren, X. Zheng, Y. Yang, S. Tang, Y. Deng, X. Meng, Appl. Catal. B Environ. 2022, 325, 122356.

[43] V. Jose, H. Hu, E. Edison, W. Manalastas Jr., H. Ren, P. Kidkhunthod, S. Sreejith, A. Jayakumar, J. M. V. Nsanzimana, M. Srinivasan, J. Choi, J.-M. Lee, Small Methods 2021, 5, 2000751.

[44] Y. Liu, T. Sakthivel, F. Hu, Y. Tian, D. Wu, E. H. Ang, H. Liu, S. Guo, S. Peng, Z. Dai, Adv. Energy Mater. 2023, 13, 2203797.

[45] Z.-Q. Liu, X. Liang, F.-X. Ma, Y.-X. Xiong, G. Zhang, G. Chen, L. Zhen, C.-Y. Xu, Adv. Energy Mater. 2023, 13, 2203609.

[46] D. S. Wang, T. Ping, Z. L. Du, X. Y. Liu, Y. X. Zhang, Nano-Micro Lett. 2025, 17, 100.

[47] D. S. Wang, T. Ping, Z. L. Du, Y. Liao, H. Gao, X. B. Gao, J. S. Rao, B. Wang, S. C. Wei, X. Y. Liu, Y. X. Zhang, Nano Res. 2025, 18, 94907226.

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2026 The Author(s). Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.